RU2459886C2 - Polyurea film and method of making said film - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: film is obtained by vacuum deposition polymerisation of an aromatic alkyl, alicyclic or aliphatic diisocyanate monomer and an aromatic alkyl, alicyclic or aliphatic diamine monomer. The diisocyanate monomer and the diamine monomer are selected from such monomers in which difference in activation energy required for the separation from a substrate is 10 Kj or less.

EFFECT: high transparency, light resistance and mass-scale productivity of the film.

8 cl, 15 dwg

Description

Technical field

The present invention relates to a polyurea film obtained on a substrate by vacuum deposition polymerization, and a method for producing it.

State of the art

Polyurea films have traditionally been obtained as a result of the interaction between diamines and diisocyanates according to the following chemical formula 1, illustrated by the methods described below in sections (a) to (d).

(a) Patent reference 1 describes a method for producing a synthetic resin film (vacuum deposition polymerization method), comprising evaporating two or more kinds of raw monomers in a processing vacuum chamber and co-polymerizing the monomers on a substrate. According to this patent reference, the feed monomers are sequentially polymerized together (polymerization condensation / polyaddition) to form a polyurea (urea resin) film comprising 4,4'-diphenylmethane diisocyanate (aromatic diisocyanate) and 4,4'-diaminodiphenyl ether (aromatic diamine) )

(b) Patent Reference 2 describes the preparation of a transparent film by polymerization in a vapor condensed layer on an ornament with a metal film or with a metal composite film. Specifically, this patent reference describes a polyurea film including 4,4'-diphenylmethane diisocyanate (aromatic series) and 4,4'-diaminophenyl ether (aromatic series) or a polyurea film including 4,4'-diphenylmethane diisocyanate (aromatic series) and 4,4'-diamino-3,3'-dimethyldiphenylmethane (aromatic series), or a polyurea film including 4,4'-diisocyanate-3,3'-dimethyldiphenyl (aromatic series) and 4,4 '-diphenylmethanediamine (aromatic series).

(c) Patent Reference 3 describes the preparation of polyurea by polymerization in a vapor condensed layer using aliphatic diisocyanate and aliphatic diamine as feed monomers. According to the patent reference herein, a polyurea film is obtained by polymerizing, for example, 1,9-diisocyanatononan (aliphatic series) and 1,9-diaminononan (aliphatic series), while maintaining a low substrate temperature (of the order of 0 ° C. or less).

(d) Patent Reference 4 states that when using a combination of low reactivity monomers, the energy required for reaction is applied to the raw monomers on a substrate to form a film. According to this patent reference, the substrate is heated in such a way as to transfer energy, while upon receipt of the polyurethane film, the temperature of the substrate leaves 90 ° C, and upon receipt of the polyester film, the temperature of the substrate leaves 130 ° C.

When producing a film from polyurea by vacuum deposition polymerization methods specific to the methods mentioned in sections (a) and (b) above, aromatic diisocyanates and aromatic diamines are usually used as raw monomers, resulting in a colorless and transparent polyurethane film. Unfortunately, with time and as a result of ultraviolet exposure, aromatic polyurea discolors (after a weather resistance test ΔE = 29.45). As shown in figure 1, unfortunately, aromatic polyurea cannot be used to obtain transparent film products, because aromatic isocyanate forms aniline as the end group of the film after interaction with water (figure 1 (a)), and then aniline interacts with oxygen to form an aniline black dye (FIG. 1 (b)), causing discoloration.

When polymerization in a layer condensed from vapors, low reactivity monomers, as in the methods mentioned above in sections (a) and (b), in contrast to the above methods, diisocyanates are used as raw material monomers to obtain a transparent film aromatic alkyl, alicyclic or aliphatic series (in structures that never form an aniline black dye). Due to the fact that these feed monomers have low reactivity, two types of such monomers may not interact, but may be deposited on a substrate so that the desired film cannot be obtained or the resulting composition is variable, which leads to the formation of uneven film. Therefore, the application of such methods to obtain products on a mass scale faces many difficulties.

In addition, because of this, when using the methods mentioned above in sections (a) and (d), the temperature of the substrate must be significantly reduced or increased. In the event that the substrate consists of a metal or inorganic material (having a high heat transfer ability without softening, plasticization and carbonization at high temperature, which are subject to resin), or if the substrate 1, clamped by the fixing device 1, is flat and thin, as shown in Fig. 2 (a) (the substrate can be evenly cooled by its fixing device or a nearby cooling source or can be evenly heated by a heating source), the temperature The cushion can be adjusted. However, if the surface of the substrate 2, as shown in FIG. 2 (b), has a so-called resin-molded product with a spatial structure, it is very difficult to maintain a constant surface temperature of the substrate or to control the temperature of the substrate.

Patent Reference 1: Publication JP-A-61-078463

Patent Reference 2: Publication JP-A-03-097849

Patent Reference 3: Publication JP-A-08-283932

Patent Reference 4: Publication JP-A-09-278805

SUMMARY OF THE INVENTION

The problem solved by the invention

The aim of this invention is to develop a film of polyurea with good transparency, light fastness and the possibility of mass production, as well as a method for its production.

Ways to solve the tasks

To solve this problem, the authors of the present invention conducted a number of studies. As a result, they found that this problem can be solved on the basis of the discovery that using a combination of a monomer of a specific diisocyanate and a specific diamine, a polyurea film with good transparency and light fastness can be obtained.

In particular, as claimed in claim 1, a polyurea film according to this invention is a polyurea film obtained by polymerization by vacuum deposition of an aromatic alkyl, alicyclic or aliphatic diisocyanate monomer and an aromatic alkyl, alicyclic or aliphatic diamine monomer, wherein the monomer diisocyanate and diamine monomer have such a ratio that the difference in activation energy between the monomers required to remove them from the substrate is Kj 10 or less.

The polyurea film according to claim 2 is a polyurea film according to claim 1, wherein the diisocyanate monomer is 1,3-bis (1-isocyanate-1-methylethyl) benzene and the diamine monomer is 1,3-bis ( aminoethyl) cyclohexane.

The polyurea film according to claim 3 is a polyurea film according to claim 1, wherein the diisocyanate monomer is 1,3-bis (isocyanatomethyl) cyclohexane and the diamine monomer is methylenebis (4-cyclohexylamine), N, N-bis - (3-aminopropyl) piperazine, 1,12-diaminododecane or 1,3-bis (aminomethyl) benzene.

The polyurea film according to claim 4 is a polyurea film according to claim 1, wherein the diisocyanate monomer is 1,3-bis (isocyanatomethyl) benzene and the diamine monomer is 1,12-diaminododecane.

As stated in claim 5, a method for producing a polyurea film according to the present invention is a method for producing a polyurea film by polymerization by vacuum deposition of an aromatic alkyl, alicyclic or aliphatic diisocyanate monomer and an aromatic alkyl, alicyclic or aliphatic diamine monomer, wherein the diisocyanate monomer and diamines have such a ratio that the difference in activation energy between the monomers required to remove them from the substrate is 10 Kj or her.

The method for producing a film from polyurea according to claim 6 is a method for producing a film from polyurea according to claim 5, in which the diisocyanate monomer is 1,3-bis (1-isocyanate-1-methylethyl) benzene, and the diamine monomer is 1, 3-bis (aminoethyl) cyclohexane.

The method for producing a film from polyurea according to claim 7 is a method for producing a film from polyurea according to claim 5, wherein the diisocyanate monomer is 1,3-bis (isocyanatomethyl) -cyclohexane and the diamine monomer is methylenebis (4-cyclohexylamine), N, N-bis- (3-aminopropyl) piperazine, 1,12-diaminododecane or 1,3-bis (aminomethyl) benzene.

The method of producing a film from polyurea according to claim 8 is a method for producing a film from polyurea according to claim 5, wherein the diisocyanate monomer is 1,3-bis (isocyanatomethyl) benzene and the diamine monomer is 1,12-diaminododecane.

Advantages of the Invention

According to this invention, a polyurea film can be obtained even for products formed from resin without changing its composition, with good transparency, hardness, toughness, resistance to chemical attack, wear resistance and strength, as well as with a spatial shape on its surface.

Brief Description of the Drawings

Figure 1 is an explanatory image explaining the cause of discoloration of known polyurea films.

Figure 2 is an explanatory view illustrating difficulties in obtaining known polyurea films.

Figure 3 is a graph illustrating the installed mass loss (TG measurement) of the monomer.

4 is a graph illustrating vapor pressure P at a temperature T of the monomer.

5 is a graph illustrating the retention time of a monomer on a substrate.

6 is a graph illustrating the relationship of the activation energies of individual monomers.

7 is a graph illustrating the relationship of the retention periods of individual monomers.

Fig. 8 is an explanatory photograph of a polyurea film in one example of the present invention.

Fig.9 is a diagram illustrating the evaluation of a variant of the example.

Character Description

1. The substrate fixing device

2. The substrate

Preferred Embodiments

According to the present invention, an aromatic alkyl diisocyanate represented by, for example, chemical formula 2, an alicyclic diisocyanate represented, for example, chemical formula 3, or an aliphatic diisocyanate represented, for example, chemical formula 4, are used as a raw material monomer diisocyanate.

Chemical formula 2

Chemical formula 3

Chemical formula 4

As a diamine as a raw material monomer, an aromatic alkyldiamine represented, for example, by chemical formula 5, an alicyclic diamine, represented by, for example, chemical formula 6, or an aliphatic diamine, represented, for example, by chemical formula 7, are used.

Chemical formula 5

Chemical formula 6

Chemical formula 7

As a result of evaporation of such raw material monomers in vacuum and the joint polymerization of monomers on a substrate, a polyurea film with good transparency and light fastness can be obtained. In addition, the vacuum pressure is not particularly limited and is usually from about 10 ⁻³ to 100 Pa.

The feed monomers are evaporated in vacuo, repeating adsorption and removal on a support. Thus, in order to form a film on the substrate, such raw material monomer is essentially subjected to interaction between each other and joint polymerization on the substrate. In other words, in the method of polymerization in a layer condensed from vapors, the retention time of the raw material monomers on the substrate (activation energy necessary for removal) and the ability to interact between raw materials (activation energy for interaction) are of great importance. Compared with a combination of monomers (aromatic series) with high reactivity (low activation energy for interaction), a combination of monomers (aromatic alkyl, alicyclic or aliphatic series) with low reactivity (high activation energy for interaction) is more strongly affected by the retention time of raw materials monomers on the substrate (activation energy required for removal). Therefore, the combination of monomers (aromatic alkyl, alicyclic or aliphatic series) with low reactivity (high activation energy for interaction) is seriously affected by a small change in any condition that affects the retention time of the raw monomers on the substrate, including the temperature of the substrate, vapor pressure of the monomers, and the temperature and degree of vacuum of the atmosphere in which the treatment occurs, due to which the polymerization of such monomers with a constant composition on the substrate causes a large t he difficulties.

Therefore, according to the present invention, such monomers are selected as follows.

Measure the mass loss of the monomer when it is heated in vacuum (TG measurement) (Fig. 3), determining the vapor pressure P (Fig. 4) at temperature T according to the Langmuir equation:

P = 228.3 m (T / M) ^1/2 ,

wherein

P = saturated vapor pressure (Pa) at temperature T;

m = evaporation rate (d∆W / dt) / U;

U = area over which evaporation takes place;

M = gram molecular weight of the evaporating molecule;

R = gas constant;

T = temperature (K) of the evaporation surface.

Then, according to the following Clausius-Clapeyron equation, the activation energy needed to eliminate (FIG. 4) and the retention time of the monomer on the substrate (FIG. 5) are determined (see “Vapor Pressure and Mean Adsorption Time of PMDA and ODA”, Japanese Journal of Applied Physics, Vol. 38 (1999), pp. L687-L690):

logP = A-ΔH / RT

τ = τ ₀ exp (Ed / RT)

ΔH / RT = activation energy;

τ = retention time (seconds); τ ₀ = 4.6 × 10 ⁻¹⁷ .

The individual monomers are selected so as to satisfy the ratio that the difference in activation energy needed to remove from the substrate between the diisocyanate monomer and the diamine monomer is 10 Kj or less (FIG. 6). In the event that the difference exceeds 10 Kj, the effect of changing the temperature of the substrate sometimes causes difficulties in obtaining a film from polyurea with a constant composition.

In other words, the individual monomers are selected so that when determining the ratio of the change in the retention time of the monomer on the substrate to the change in the temperature of the substrate, the difference in the ratio of changes between the monomer with a similar small volume of changes and the monomer with a similar large volume of changes is 20% or less (Fig. 7) .

As shown in the figure illustrating a specific monomer, in particular, the reciprocal of the temperature of the substrate, namely, 1 / T (K ^-1 ), is presented on the transverse axis, while the longitudinal axis represents the retention time of the monomer on the substrate, namely , τ (sec). Then determine the angular k of the graph, namely (τ / (1 / T)). The angular k1 of the graph of the diisocyanate monomer used in vacuum deposition is determined, as well as the angular k2 of the diamine monomer used in it (in this description, it is assumed that k1>k2; thus, k1 represents the basic ratio of the changes). In the event that [1- (k1-k2)] is 20% or less, a diamine monomer with k2 is selected for the diisocyanate monomer with k1.

Due to the combination of the diisocyanate monomer and the diamine monomer selected by the above two methods, a film with a uniform composition can be obtained from such raw monomers with a low reactivity without the need to control the temperature of the substrate or without any influence of inter-series conditions (for example, the conditions between the first and second film production), such as the vapor pressure of the monomer, as well as the temperature and degree of vacuum of the atmosphere for processing.

As the raw material monomer according to this invention, any raw material satisfying the above conditions can be used, without specific restrictions. The following are specific examples of such monomers.

Diisocyanates

Aromatic alkyl: 1,3-bis (isocyanatemethyl) benzene, 1,3-bis (1-isocyanate-1-methylethyl) benzene, etc.

Alicyclic: 1,3-bis (isocyanatemethyl) cyclohexane, 3-isocyanatemethyl-3,5,5-trimethylhexyl isocyanate, methylene bis (4-cyclohexyl isocyanate), 2,5 (2,6) -bis (isocyanatemethyl) bicyclic [2,2, 1] heptane, etc.

Aliphatic: 1,6-diisocyanatehexane, 1,5-diisocyanate-2-methylpentane, 1,8-diisocyanatoctane, 1,12-diisocyanate dodecane, tetraisocyanatesilane, monomethyltriisocyanatesilane, etc.

Diamines

Aromatic alkyl: 1,3-bis (aminomethyl) benzene,

1,4-bis (aminoethyl) benzene, isophthalic acid dihydrazide, etc.

Alicyclic: 1,3-bis (aminomethyl) cyclohexane,

1,4-bis (aminomethyl) cyclohexane, 3-aminomethyl-3,5,5-trimethylhexylamine, 1,2-diaminecyclohexane, 1,4-diaminecyclohexane, methylenebis (4-cyclohexylamine), piperazine, 2-piperazine, 2,5 -dimethylpiperazine, 2,6-dimethylpiperazine, N, N'-bis- (3-aminopropyl) piperazine, 1,3-di (4-piperidyl) propane, hydantoin, hexahydro-1H-1,4-diazepine, barbituric acid and etc.

Aliphatic: 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminooctane, 1,10-diaminooctane, 1,12-diaminododecane, bis (2-aminoethyl) amine, bis (3- aminopropyl) amine, N, N'-bis (aminopropyl) methylamine, N- (3-aminopropyl) -1,4-butanediamine, N, N '- (3-aminopropyl) -1,4-butanediamine, adipic acid dihydrazide, dodecane acid dihydrazide, sebacic acid dihydrazide, etc.

Examples

In order to establish that the difference in the retention time of the feed monomer on the substrate affects the film production by determining the vapor pressure P at temperature T (on the vapor pressure curve), as well as the activation energy required to remove it from the substrate, based on the measurement results of the loss masses when heating the monomer in vacuum, to obtain films of polyurea in examples 1-6 and comparative example 1, combinations of diisocyanates and diamines were used.

Example 1

Diisocyanate: 1,3-bis (1-isocyanate-1-methylethyl) benzene

Diamine: 1,3-bis (aminomethyl) cyclohexane

Example 2

Diisocyanate: 1,3-bis (isocyanatomethyl) cyclohexane

Diamine: methylenebis (4-cyclohexylamine)

Example 3

Diisocyanate: 1,3-bis (isocyanatomethyl) cyclohexane

Diamine: N, N-bis (3-aminopropyl) piperazine

Example 4

Diisocyanate: 1,3-bis (isocyanatomethyl) cyclohexane

Diamine: 1,12-diaminododecane

Example 5

Diisocyanate: 1,3-bis (1-isocyanatemethyl) cyclohexane

Diamine: 1,3-bis (aminomethyl) benzene

Example 6

Diisocyanate: 1,3-bis (isocyanatomethyl) benzene

Diamine: 1,12-diaminododecane

Comparative Example 1

Diisocyanate: 1,3-bis (isocyanatomethyl) benzene

Diamine: methylenebis (4-cyclohexylamine)

The results of the experimental preparation of films in examples 1-6 and comparative example 1 are presented in the table.

The quality of the film Transparency Light strength Mass productivity The difference in activation energy for removal (kJ) Appearance The difference in composition between samples CV% Gear ratio% ∆Е The difference in composition between samples CV% Example 1 0.1 ○ 5.14 More than 80 1.8 5.82 Example 2 0.2 ○ 7.90 More than 80 0.4 5.44 Example 3 0.3 ○ 7.24 More than 80 0.8 4.29 Example 4 5,6 ○ 9.47 More than 80 0.5 4.87 Example 5 9.2 ○ 28.43 More than 80 1,5 50.68 Example 6 5.1 ○ 10.21 More than 80 1.3 17.63 Compares.
example 1 10.5 x 85.62 - - -

Based on the assessment of the appearance, it was found that films of polyurea were obtained in examples 1-6, while in comparative example 1, as shown in Fig. 8, regions with a film and regions without a film were obtained.

Regarding the estimation of the difference in the film composition at 10 points of the same sample, a large difference in the film composition was observed as the difference in the activation energy for removal between the raw monomers in combination increased. The difference in the composition of the film is determined by comparing the ratio of the absorption area of isocyanate (-NCO) with the absorption area of amine (-NH ₂ ) at 10 points on the IR graphs obtained by measuring FT-IR (IR spectrometer with Fourier transform) immediately after receiving the film (see Fig.7).

Based on the assessment of the appearance and study of the difference in the composition of the film, it was found that the difference in the retention time of the raw monomer on the substrate (activation energy necessary to eliminate) affects the production of the film.

As for possible combinations for obtaining various types of films, transparency, lightfastness, and mass productivity were additionally investigated. The results are presented in the table. Transparency is determined by measuring the transmission ratio of the sample with a film thickness of 20 μm with an absorometer within the visible spectrum (from 400 to 800 nm). Weather resistance is determined by placing the sample in an accelerated light-tightness test with a carbon-arc lamp for 400 hours and measuring the color difference before and after the test. Mass productivity is determined by comparing the difference in film composition in one series (the difference between the first and second film compositions ...) and in all ten tests based on the results of measurements using FT-IR.

It was found that when the difference in activation energies required to remove the raw monomers in combination is 10 kJ or less, polyurea films with excellent transparency, lightfastness, and mass productivity can be obtained.

It was found that the application of the method for producing the film described in example 1, provides a film with a uniform composition without using any mechanism to control the temperature of the substrate or without using any mechanism to eliminate the influence of the device or the environment for such production (vapor pressure monomer, temperature and degree of vacuum in the chamber for obtaining the film) between the series (between the first and second receipt of the film ...) in the device for such receipt.

Claims (8)

1. A polyurea film obtained by polymerization by vacuum deposition of an aromatic alkyl, alicyclic or aliphatic diisocyanate monomer and an aromatic alkyl, alicyclic or aliphatic diamine monomer, while the diisocyanate monomer and diamine monomer are selected so that the difference in activation energy between them removal from the substrate is 10 kJ or less. 2. The polyurea film according to claim 1, wherein the diisocyanate monomer is 1,3-bis (1-isocyanate-1-methylethyl) benzene and the diamine monomer is 1,3-bis (aminoethyl) cyclohexane. 3. The polyurea film according to claim 1, wherein the diisocyanate monomer is 1,3-bis (isocyanatomethyl) -cyclohexane and the diamine monomer is methylenebis (4-cyclohexylamine), N, N-bis- (3-aminopropyl) piperazine, 1,12-diaminododecane or 1,3-bis (aminomethyl) benzene. 4. The polyurea film according to claim 1, wherein the diisocyanate monomer is 1,3-bis (isocyanatomethyl) benzene and the diamine monomer is 1,12-diaminododecane. 5. A method of producing a polyurea film by polymerization by vacuum deposition of an aromatic alkyl, alicyclic or aliphatic diisocyanate monomer and an aromatic alkyl, alicyclic or aliphatic diamine monomer, wherein the diisocyanate monomer and diamine monomer are selected so that the difference in activation energy between the monomers is necessary removal from the substrate is 10 kJ or less. 6. The method for producing a polyurea film according to claim 5, wherein the diisocyanate monomer is 1,3-bis (1-isocyanate-1-methylethyl) benzene and the diamine monomer is 1,3-bis (aminoethyl) cyclohexane. 7. The method of producing a film from polyurea according to claim 5, in which the diisocyanate monomer is 1,3-bis (isocyanatomethyl) cyclohexane, and the diamine monomer is methylenebis (4-cyclohexylamine), N, N-bis- (3-aminopropyl ) piperazine, 1,12-diaminododecane or 1,3-bis (aminomethyl) benzene. 8. The method of producing a film from polyurea according to claim 5, in which the diisocyanate monomer is 1,3-bis (isocyanatomethyl) benzene, and the diamine monomer is 1,12-diaminododecane.

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